CN1184488A - Anti-scaling agent for coating of polymerization reactors and preparation process thereof - Google Patents
Anti-scaling agent for coating of polymerization reactors and preparation process thereof Download PDFInfo
- Publication number
- CN1184488A CN1184488A CN96193870A CN96193870A CN1184488A CN 1184488 A CN1184488 A CN 1184488A CN 96193870 A CN96193870 A CN 96193870A CN 96193870 A CN96193870 A CN 96193870A CN 1184488 A CN1184488 A CN 1184488A
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- scale inhibitor
- coating
- polymerization reactors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The object of the invention is to provide a procedure for the anti-scaler production for coating the reactors of polymerizing for monomers, of the types obtained by means of the napththols condensation with an aldehydic cross-linking product, characterized in the fact that said aldehydic product is a product that comes from the reaction between an aldehyde and hydrosulphite.
Description
Technical field
The present invention relates to be used for the preparation method and the product obtained by this method of the scale inhibitor of coating of polymerization reactors.
The polymerization reactor scale inhibitor is that prior art is known.
Background technology
In this area, all there is different types of scale inhibitor for each polymkeric substance.
The scale inhibitor of using when for example, producing vinylchlorid when producing polystyrene in reactor used scale inhibitor or during with the production acrylate copolymer in the reactor used scale inhibitor etc. be inequality.
This statement of facts need be stored different products, and consequently handling cost increases.
In addition, in addition reactor also must be specifically ad hoc at a kind of reaction type only, this also causes cost to improve.
Description of the invention
First purpose of the present invention is a kind of scale inhibitor of preparation, and this scale inhibitor can both work well for the polymerization reactor of any kind, and is applicable to various dissimilar raw materials, therefore also is applicable to vinylchlorid, vinylbenzene and acrylate copolymer etc.
For the such particular case of for example vinylchlorid, a large amount of bird nest of deposition can produce following main drawback in reactor as everyone knows:
-need safeguard consistently for removing bird nest, consequently produce and interrupt, open reactor, therefore have a large amount of gaseous vinyl chloride monomers (VCM) and spill in the atmosphere;
-when entering into corresponding polymerisate, some bird nest fragments can pollute end product, the degradation of product consequently, and the user is dissatisfied;
-in polyvinyl chloride factory (P.V.C.) output zone of industry, aspect production system and ecological problem, produce serious problems.
These problems almost are present in all types of polyreactions.
And, the scale inhibitor that appointment is used for applying corresponding reactor surface is blueness or the chocolate that is similar to black, a material that strips down from the top layer thus will pollute the polymkeric substance (polyvinyl chloride that for example obtains) that obtains from reactor, particle is the form of black spots point in polymkeric substance, this just feasible for example degradation of the described product in finished product.
And should be noted that: the feed particles that strips down from the top layer of reactor wall finally falls into the product of reaction, constitutes the pollution of the said products, also relates to poisonous product usually.
Known in the prior art by the condensation technology or from naphthols and aldehyde cross-linking products (for example formaldehyde and other material) polycondensation and can obtain the antiscale product.
This paper quotes for this reason:
The mixture of US-A-3669946 (on August 31st, 1970, on June 13rd, 1972 was open at U. S. application) suggestion use formaldehyde and ketone, naphthols etc. or alpha-naphthylamine and nigrosine.This technology discloses the universal that forms condensation scale inhibitor product with the mixture of formaldehyde and naphthols.
US-A-3825434 (on July 23rd, 1974) has described a kind of scale inhibitor that is used for chloroethylene polymerization, this scale inhibitor obtains with phenol and formaldehyde condensation, obviously for ease of setting forth, in this patent, products therefrom is categorized in the family relevant with phenolic aldehyde or poly-aryl phenol (Poliarilphenol) herein.
US-4, the importance of using scale inhibitor has further been explained in 068,059 (application on February 17th, 1977, on January 10th, 1978 is open), contains one or more following groups :-OH in the chemical structure of this scale inhibitor product;-COOH;-SO
3H and-SO
3Na.These groups are usually located on the aromatic ring.
EP-A-0052421 has described the method that obtains the antiscale product, this product different situations be: the reaction of formaldehyde and 1-naphthols (naphthyl alcohol) is obtained condenses, and on the ring 2 and 43 of not being substituted and encircling are not substituted or have the naphthols that is not strong electron-withdrawing substituent all is effective.
By chance be also noted that: US-A-3669946 has proposed to use naphthols, and it is conspicuous therefore substituting the phenol of being mentioned with the 1-naphthols in aforesaid method.
Even in this case, it is relevant with poly-aryl phenol family that the product that obtains according to chemical process still always is considered to.
The shortcoming of these existing procucts is with after oxygen contacts, and obtains being similar to the chocolate or the blue-black product of black, and always is not suitable in the polyreaction of different material.
Sometimes reaction is not allow manageablely, and the netted product that causes being insoluble to alkaline aqueous solution generates.
And the coating that has scale inhibitor on the reactor is consumed easily and is dispersed in the reaction raw materials, pollutes reaction raw materials from color and toxicity aspect.
And must be pointed out, the effect of these scale inhibitors is not good, it makes and deposit a large amount of bird nests on reactor wall in other words, thereby has limited the application of some application as aspects such as health and food, requires the pollutant load in the finished product will hang down without doubt in these areas
For obtaining good antiscale effect, must on reactor wall, deposit a large amount of scale inhibitors, this has also just influenced product cost.
The color of the scale inhibitor of known technology is a black, and this color is that the user is inappreciative, also because it makes the people expect pollution products.
Therefore the black of product makes that the top layer on the reactor wall also is (blackish) of black, makes people can't see defective in the contingent application.But even more serious is that as already mentioned, in reaction process, the top layer particle is peeled off and and mixed with polymers.Because the top layer part is deceived, and obviously makes the downgrade of product.
The objective of the invention is to eliminate above-mentioned shortcoming, especially eliminate the black of product and the black on the top layer that will on reactor wall, form.
The contriver wants to prepare a kind of antiscale product, and in a single day this product is coated on the reactor wall is colourless basically just.
Know, bleach, can use V-Brite B (hydrosulphite sodium) or potassium hyposulfite for making aromatic product (if any pigmentation).
The contriver wants this common bleaching principle is migrated in the preparation of scale inhibitor, to obtain required colorless product.
Attempt to use hyposulfite and together with using formaldehyde and 1-naphthols, the result who obtains is negative, and is black-and-blue because condensation product always keeps, be easy to form precipitation, even also be like this there not being oxygen for example under nitrogen atmosphere, to carry out condensation reaction.
In research subsequently, expect avoiding the reaction between formaldehyde and the 1-naphthols, therefore make formaldehyde use the aldehydes goods that can obtain colourless condensation product for avoiding.
Through after the countless experiments, find that combining best product with the 1-naphthols is rhongalite.
The result is astonishing, and the condensation product that is obtained is perfect colourless product.
In the tartar preventing test of pvc response device, no matter be performance, quality or productive rate, the result of gained is surprising, this scale inhibitor also can be used in the production of other polymkeric substance.
Rhongalite is a kind of trade(brand)name of the universal product, chemically it is defined as formaldehyde-sodium hydrosulfite 90min, and general formula is:
This product obtains hyposulfite and formaldehyde reaction, so this product has been a formaldehyde no longer.
Because this reason, condensation product therefore no longer be black-and-blue or even black, obviously be because to produce the instruction of scale inhibitor opposite with prior art, prevented the principal reaction between 1-naphthols and formaldehyde.
Find that at last the feature of employed aldehyde cross-linking agent is that it must be the product that aldehyde and SODIUM HYDROSULPHITE reactant salt obtain.
Adopt this sulfenic acid product and 1-naphthols composition mixture, the weight ratio that makes both is 1 to 1.5, and the percentage ratio of mixture in the aqueous solution is 10-40%.This solution is maintained between 70 ℃-95 ℃ under nitrogen atmosphere alkaline environment (pH is 11-13), obtain as clear as crystal condensation product thus, reach preassigned target fully, do not reduce the quality of product, in fact also improved the quality of product.
The condensation product that obtains in this way is actually as clear as crystal, if but in air, place for some time, this product can be become blue-greenish colour by mild oxidation.
Yet curious is that if make this condensation product stop to separate with connecing of oxygen, product returns to its original as clear as crystal state again.
This physical behavior proves, compares with product of the prior art, and the inventor has obtained different product on a kind of fully new and structure, and this physical phenomenon that product of the present invention occurred be can't see in the product of prior art.
By chemistry and spectroscopic analysis, the constitutional features of this product has been proposed various hypothesis, but has not also had its structure of full confirmation, the someone thinks that the reversibility of this phenomenon is owing to have reducing activity in the condenses, may be because have the reduction group to exist so.
At last, according to more possible deduction, it should relate to the bisulfite addition product of first product that reaction forms between 1-naphthols and the rhongalite.
This product is coated to reactor surface in the atmosphere of having removed oxygen, after the drying, the coating that obtains is opaque oyster white, is the opposite of black with scale inhibitor of the prior art.
The result who obtains thus is good surprisingly.
In order to make product liquid before being coated on the reactor wall, keep vitreous state,, it should be kept in the container of oxygen flow not according to the present invention.
Find that best preserving type is that container is preferably used the nitrogen high pressure seal with neutral gas.
Find that the most effective container is to make (free from environmental pollution with the container that this material is made, and can all reclaim) with glass or polyethylene terephthalate " PET ".
When using the container (flexible container) that " PET " make, found the physical behavior that another is important:
Product according to the present invention looks like when airtight transparently tight, and after for example this product of liter flask being opened and opened wide several minutes in air, the product of being contained becomes black;
Again that bottle is airtight after product becomes black, find that flexible " PET " bottle has slight contraction.Can think that its reason is that product has consumed and is retained in the contained airborne oxygen of opening originally on now airtight again of bottle.
After this product changes into as preceding as clear as crystal color again, just look like not take place whatever.
This just proves that this product itself has autoprotection, but perhaps it not with condition that air contacts under automatic reconstituting become its original structure.
Preserve described product, the as clear as crystal color that makes it to remain unchanged, and in the experiment on being coated to reactor wall (obviously being in the presence of rare gas element), scale inhibitor is deposited as very thin one deck on reactor wall, this coating is colourless and transparent as previously mentioned.
Finding preferably will be with this product in the environment of anaerobic, and is coated on the reactor wall by the mode of high-temperature water vapor spraying.
By spraying this product, obtain having the coating of maximum adhesion power with high temperature (top temperature as much as possible) water vapor.
Because the polyreaction in the reactor on average continues 4 to 6 hours, obviously during this period of time, under the situation that anaerobic exists, this product can not decompose basically and colorimetric (colorimetric) is subsequently decomposed, in case polyreaction is finished thus, in case the antiscale product of minimum is incorporated in the polymer material, will further important pollution and decomposition take place no longer.
Yet in using the prior art of known in the past antiscale product, people's reactor of having to scrub fully and soar is to remove the residue that is applied to any minimum trace of the product on the reactor wall as scale inhibitor.When using product innovation of the present invention, the flushing thing of reactor can be delivered to collect has in the container of polymer slurry, and no longer needs further to discharge residue.Realized a kind of complete, effective especially economic technology in this way, this technology is that the method for utilizing those skilled in the art to be called closed manhole (man hole closed) is come the polymerization reactor charging of vinyl chloride monomer and the technology of discharging.
Because the rhongalite also hyposulfite of available molar excess makes, even by using this product can obtain the condenses (being the reductive condenses basically) of similar performance or improvement performance.
It seems from the situation of situation of the present invention and prior art, product activity is to be given by the bisulfite salt derivative that exists, the bisulfite group that particularly is present in the condenses, this feature clearly differentiates product innovation of the present invention and prior art, during especially with reference to the final structure of condensation product, the insertion carbon atom that exists between aromatic ring and salify sulfonic group is considered to novel.
The result who uses the alternative 1-naphthols of other naphthols to obtain is similar substantially, and this point also is confirmed.
Obviously for aforementioned purpose, not with formaldehyde and V-Brite B reaction obtaining rhongalite, and can make formaldehyde and SODIUM HYDROSULPHITE nak response, obtain being used to form effectively the product of condenses equally.
Yet importantly, hydrosulphite has prevented to react towards the direction of stable condensed forms to develop.
Claims (16)
1. apply the preparation method of the scale inhibitor of monomer polymerization reactions device, this scale inhibitor is obtained by naphthols and the condensation of aldehyde cross-linking products, it is characterized in that described aldehyde cross-linking products is the product that aldehyde and SODIUM HYDROSULPHITE reactant salt obtain.
2. be used to be coated to the liquid scale inhibitor product on the polyreaction wall, make, it is characterized in that according to the method for claim 1:
When no oxygen existed, the color of scale inhibitor was as clear as crystal, and if
When having oxygen to exist, scale inhibitor becomes blue-greenish colour or black; And if
After stopping the contacting of scale inhibitor and oxygen, it returns to its original situation again.
3. according to the product of claim 2, make according to the method for claim 1, it is characterized in that this product contains the bisulfite group.
4. scale inhibitor product makes according to the method for claim 1, it is characterized in that this product contains hyposulfite.
5. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that in reaction, having added V-Brite B.
6. the preparation method of the scale inhibitor of coating of polymerization reactors is characterized in that having added potassium hyposulfite in reaction.
7. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that the scale inhibitor product is stored in the container of oxygen flow not.
8. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that the scale inhibitor product is stored in the container with the not oxygen flow of rare gas element pressurization.
9. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that the scale inhibitor product is stored in the container with the not oxygen flow of nitrogen pressure.
10. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that the scale inhibitor product is stored in the container with the not oxygen flow of nitrogen pressure, described container adopts polyethylene terephthalate (PET) to make.
11. preparation method according to the scale inhibitor of the coating of polymerization reactors of claim 1, it is characterized in that the product that contains hyposulfite adds in such a manner, make that these hyposulfite are prevented and react and develop towards the direction that forms stable condenses.
12. the preparation method according to the scale inhibitor of the coating of polymerization reactors of claim 1 is characterized in that the addition of hyposulfite is carried out under alkaline condition.
13. according to the preparation method of the scale inhibitor of the coating of polymerization reactors of claim 1, the addition that it is characterized in that hyposulfite is to carry out under the alkaline condition of about 11-13 at pH.
14. according to the scale inhibitor product that is used for coating of polymerization reactors of aforementioned claim, it is characterized in that this product is stored in the container with the not oxygen flow of nitrogen pressure, described container adopts polyethylene terephthalate (PET) to make.
15., it is characterized in that this product is stored in the container with the not oxygen flow of nitrogen pressure the transparent vessel of described container for being made by polyethylene terephthalate (PET) according to the scale inhibitor product that is used for coating of polymerization reactors of aforementioned claim.
16., it is characterized in that it contains the hydrosulphite vestige according to the scale inhibitor product that is used for coating of polymerization reactors of aforementioned claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITUD95A000085 | 1995-05-12 | ||
| IT95UD000085A IT1280167B1 (en) | 1995-05-12 | 1995-05-12 | PROCEDURE FOR THE PRODUCTION OF ANTI-INCROSTANT TO COAT THE POLYMERIZATION REACTORS AND THE RESPECTIVE RESULTING PRODUCT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184488A true CN1184488A (en) | 1998-06-10 |
| CN1106405C CN1106405C (en) | 2003-04-23 |
Family
ID=11421826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96193870A Expired - Fee Related CN1106405C (en) | 1995-05-12 | 1996-05-07 | Anti-scaling agent for coating of polymerization reactors and preparation process thereof |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US5888589A (en) |
| EP (1) | EP0824549B1 (en) |
| JP (1) | JP3603309B2 (en) |
| KR (1) | KR100408839B1 (en) |
| CN (1) | CN1106405C (en) |
| AT (1) | ATE272075T1 (en) |
| AU (1) | AU715094B2 (en) |
| BR (1) | BR9608870A (en) |
| CA (1) | CA2220227C (en) |
| DE (1) | DE69633010T2 (en) |
| ES (1) | ES2225883T3 (en) |
| HU (1) | HU224522B1 (en) |
| IT (1) | IT1280167B1 (en) |
| MX (1) | MX9708738A (en) |
| NO (1) | NO315376B1 (en) |
| PL (1) | PL198490B1 (en) |
| RO (1) | RO120149B1 (en) |
| WO (1) | WO1996035723A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1280168B1 (en) * | 1995-05-12 | 1998-01-05 | Cirs Spa | ANTI-INCROSTANT TO COAT THE POLYMERIZATION REACTORS AND THE RESPECTIVE RESULTING PRODUCT |
| IT1280181B1 (en) * | 1995-06-05 | 1998-01-05 | Cirs Spa | PROCEDURE FOR THE PRODUCTION OF ANTI-INCROSTANT TO COAT THE POLYMERIZATION REACTORS AND THE RESPECTIVE RESULTING PRODUCT |
| US6525457B1 (en) | 2000-09-21 | 2003-02-25 | Samsung Sdi Co., Ltd. | Tensioned shadow mask assembly for flat cathode ray tube |
| JP3974882B2 (en) | 2003-08-07 | 2007-09-12 | 信越化学工業株式会社 | Polymer scale adhesion inhibitor |
| US6906129B2 (en) | 2003-09-05 | 2005-06-14 | Shin-Etsu Chemical Co., Ltd. | Polymer scale preventive agent |
| ITUD20100097A1 (en) * | 2010-05-20 | 2011-11-21 | Alchemia Italia Srl | "PROCEDURE FOR THE PREPARATION OF AN ANTI-INCROSTATING AGENT FOR PVC REACTORS AND ANTI-INCORSTANT AGENT FOR PVC REACTORS SO OBTAINED" |
| EP2581421A1 (en) | 2011-10-12 | 2013-04-17 | Ineos Europe AG | Additive |
| DE102015202580A1 (en) * | 2015-02-12 | 2016-08-18 | Wacker Chemie Ag | Process for the polymerization of ethylenically unsaturated monomers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE94210C (en) * | 1970-05-07 | |||
| US3825434A (en) * | 1972-10-27 | 1974-07-23 | Goodrich Co B F | Internally coated reaction vessel and process for coating the same |
| JPS5230112A (en) * | 1975-09-02 | 1977-03-07 | Sanyo Denshi Kogyo Kk | Offset beat canceller |
| US4068059A (en) * | 1977-02-17 | 1978-01-10 | The B. F. Goodrich Company | Internally coated reaction vessel for use in olefinic polymerization |
| ATE23866T1 (en) * | 1980-10-31 | 1986-12-15 | Ici Plc | VINYL CHLORIDE POLYMERIZATION PROCESS. |
| JPH05230112A (en) * | 1992-02-24 | 1993-09-07 | Shin Etsu Chem Co Ltd | Agent for preventing deposition of polymer scale, polymerizer effective in preventing deposition of polymer scale and production of polymer using the polymerizer |
| ES2097461T5 (en) * | 1992-11-10 | 2003-04-16 | Shinetsu Chemical Co | IMPEDITIVE AGENT OF POLYMER INCRUSTATIONS. |
| IT1280168B1 (en) * | 1995-05-12 | 1998-01-05 | Cirs Spa | ANTI-INCROSTANT TO COAT THE POLYMERIZATION REACTORS AND THE RESPECTIVE RESULTING PRODUCT |
-
1995
- 1995-05-12 IT IT95UD000085A patent/IT1280167B1/en active IP Right Grant
-
1996
- 1996-05-07 CA CA002220227A patent/CA2220227C/en not_active Expired - Fee Related
- 1996-05-07 WO PCT/IT1996/000092 patent/WO1996035723A1/en active IP Right Grant
- 1996-05-07 HU HU9901064A patent/HU224522B1/en not_active IP Right Cessation
- 1996-05-07 DE DE69633010T patent/DE69633010T2/en not_active Expired - Lifetime
- 1996-05-07 MX MX9708738A patent/MX9708738A/en unknown
- 1996-05-07 RO RO97-02096A patent/RO120149B1/en unknown
- 1996-05-07 ES ES96914380T patent/ES2225883T3/en not_active Expired - Lifetime
- 1996-05-07 EP EP96914380A patent/EP0824549B1/en not_active Expired - Lifetime
- 1996-05-07 CN CN96193870A patent/CN1106405C/en not_active Expired - Fee Related
- 1996-05-07 AT AT96914380T patent/ATE272075T1/en not_active IP Right Cessation
- 1996-05-07 AU AU57773/96A patent/AU715094B2/en not_active Ceased
- 1996-05-07 KR KR1019970708062A patent/KR100408839B1/en not_active IP Right Cessation
- 1996-05-07 PL PL323464A patent/PL198490B1/en unknown
- 1996-05-07 US US08/952,087 patent/US5888589A/en not_active Expired - Lifetime
- 1996-05-07 JP JP53393096A patent/JP3603309B2/en not_active Expired - Fee Related
- 1996-05-07 BR BR9608870A patent/BR9608870A/en not_active IP Right Cessation
-
1997
- 1997-11-03 NO NO19975052A patent/NO315376B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990014720A (en) | 1999-02-25 |
| AU5777396A (en) | 1996-11-29 |
| DE69633010D1 (en) | 2004-09-02 |
| IT1280167B1 (en) | 1998-01-05 |
| NO975052L (en) | 1997-12-11 |
| EP0824549B1 (en) | 2004-07-28 |
| AU715094B2 (en) | 2000-01-13 |
| JPH11505557A (en) | 1999-05-21 |
| RO120149B1 (en) | 2005-09-30 |
| HU224522B1 (en) | 2005-10-28 |
| KR100408839B1 (en) | 2005-02-24 |
| BR9608870A (en) | 1999-06-15 |
| EP0824549A1 (en) | 1998-02-25 |
| PL323464A1 (en) | 1998-03-30 |
| PL198490B1 (en) | 2008-06-30 |
| MX9708738A (en) | 1997-12-31 |
| JP3603309B2 (en) | 2004-12-22 |
| CA2220227A1 (en) | 1996-11-14 |
| CA2220227C (en) | 2002-04-16 |
| US5888589A (en) | 1999-03-30 |
| ES2225883T3 (en) | 2005-03-16 |
| DE69633010T2 (en) | 2005-07-21 |
| WO1996035723A1 (en) | 1996-11-14 |
| ITUD950085A0 (en) | 1995-05-12 |
| HUP9901064A3 (en) | 1999-11-29 |
| ATE272075T1 (en) | 2004-08-15 |
| HUP9901064A1 (en) | 1999-07-28 |
| ITUD950085A1 (en) | 1996-11-12 |
| NO315376B1 (en) | 2003-08-25 |
| CN1106405C (en) | 2003-04-23 |
| NO975052D0 (en) | 1997-11-03 |
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